A surprisingly high first vertical ionization energy (8.44 eV) and an unusually high oxidation potential are exibited by tricyclopropylamine (1)—in sharp contrast to triisopropylamine. These are attributed to the near-tetrahedral geometry of 1 at the N atom and the perpendicular orientation—with respect to the N-orbital axis—of the cyclopropyl groups. γ-Irradiation of 1 led to the radical cation 1.+, which, in accord with computations, has a planar C3h-symmetrical structure. The EPR-spectroscopic and computational results disclose a dramatic, previously not reported, conformational change on going from 1 to 1.+.